全文获取类型
收费全文 | 442篇 |
免费 | 26篇 |
国内免费 | 103篇 |
专业分类
化学 | 555篇 |
晶体学 | 2篇 |
物理学 | 14篇 |
出版年
2024年 | 1篇 |
2023年 | 10篇 |
2022年 | 15篇 |
2021年 | 12篇 |
2020年 | 20篇 |
2019年 | 18篇 |
2018年 | 14篇 |
2017年 | 10篇 |
2016年 | 30篇 |
2015年 | 14篇 |
2014年 | 18篇 |
2013年 | 80篇 |
2012年 | 18篇 |
2011年 | 16篇 |
2010年 | 15篇 |
2009年 | 21篇 |
2008年 | 24篇 |
2007年 | 34篇 |
2006年 | 28篇 |
2005年 | 19篇 |
2004年 | 32篇 |
2003年 | 24篇 |
2002年 | 9篇 |
2001年 | 12篇 |
2000年 | 12篇 |
1999年 | 9篇 |
1998年 | 1篇 |
1997年 | 10篇 |
1996年 | 4篇 |
1995年 | 4篇 |
1994年 | 6篇 |
1993年 | 7篇 |
1992年 | 1篇 |
1991年 | 5篇 |
1990年 | 3篇 |
1989年 | 5篇 |
1987年 | 3篇 |
1986年 | 2篇 |
1985年 | 1篇 |
1984年 | 1篇 |
1983年 | 1篇 |
1981年 | 1篇 |
1972年 | 1篇 |
排序方式: 共有571条查询结果,搜索用时 15 毫秒
1.
Dongping Wang Jie Dong Wenjing Fan Prof. Dr. Xiang-Ai Yuan Prof. Dr. Jian Han Prof. Dr. Jin Xie 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(22):8508-8512
An unprecedented Mn(I)-catalyzed selective hydroarylation and hydroalkenylation of unsaturated amides with commercially available organic boronic acids is reported. Alkenyl boronic acids have been successfully employed for the first time in Mn(I)-catalyzed carbon–carbon bond formation. A wide array of β-alkenylated amide products can be obtained in moderate to good yields, which offers practical access to five- and six-membered lactams. This protocol has predictable regio- and chemoselectivity, excellent functional group compatibility and ease of operation in air, representing a significant step-forward towards manganese-catalyzed C−C coupling. 相似文献
2.
Xuyuan GuScott Cowell Jinfa YingXuejun Tang Victor J. Hruby 《Tetrahedron letters》2003,44(31):5863-5866
(2S,3S)- and (2R,3R)-2-amino-3-phenyl-5-hexenoic acids have been synthesized in large scale by using Ni(II)-complexes as a template. The amino acids were used in the synthesis of [4,3,0]-bicyclic β-turn mimetics by a convergent methodology. The unique advantage of this strategy is the convenience of introducing side chain groups with predetermined chiralities on both the five- and six-membered heterocyclic rings. 相似文献
3.
Alpeshkumar K. Malde Santosh A. Khedkar Evans C. Coutinho 《Journal of Physical Organic Chemistry》2007,20(2):151-160
Modification of peptides to produce peptidomimetics is of great interest, with the aim of designing potent, selective, and metabolically stable analogs having certain conformational properties. Organoboranes have been reported in the literature with a wide range of therapeutic applications. One of the therapeutically important class of molecules is amine‐carboxyboranes derived from amino acids by replacement of the Cα atom of an amino acid/peptide by boron. The conformational preferences of these peptides, with respect to backbone ω, ?, and ψ torsion angles, have been investigated by theoretical calculations. The amide bond in these molecules has the same geometry in the ground and transition states as the natural peptides. However, the boron isosteres of glycine and alanine peptides are less structured than their natural derivatives, but are distinguished by structures with a positive value for the ? angle, which is normally disfavored for natural peptides. This property could be used to build peptides with a geometry not usually seen in natural peptides. Copyright © 2007 John Wiley & Sons, Ltd. 相似文献
4.
5.
6.
微波促进下N,N-二甲基甲酰胺中的Knoevenagel反应 总被引:2,自引:0,他引:2
在微波促进下,芳醛与丙二腈或氰基乙酸乙酯在DMF中进行Knoevenagel缩合反应,以77%~98%的产率生成相应E-式烯烃。 相似文献
7.
8.
Prochiral alkenes, aldehydes, and ketones constitute the most frequently used starting materials for enantioselective organic syntheses. Protocols often involve chiral binding agents or Lewis acids that can give two diastereomeric adducts, the ratios of which are measures of chiral recognition. With π adducts, the diastereomers differ in the enantioface of the C?C or O?C group bound to the Lewis acid. This review provides the first comprehensive analysis of such equilibria and related binding phenomena with chiral transition metal Lewis acids. An extensive body of data from the authors' laboratory for complexes of the pyramidal rhenium fragment [(η5?C5H5)Re(No)(PPh3)]+ ( I ) affords particular insight. Literature data for other complexes are also summarized. A general model for chiral recognition based upon the relative steric properties of four quadrants is presented. This enables binding selectivities to be individually and rationally optimized for different classes of ligands. Electronic effects are also identified and correlated with specific structural properties. Relationships between binding equilibria, reactivity, and product configurations are discussed. 相似文献
9.
With the assistance of HPLC-ESI-MS/MS, the self-assembly products of serine and histidine penta-coordinated phosphorus compound were separated and identified. The expectative product was seryl-histidine dipeptide, but it was found that there was almost equimolar amount of histidyl-histidine dipeptide as well as seryl-histidine dipeptide. The mechanism was speculated that there was iigand exchange between penta-coordinated phosphoryl serine and histidine in the reaction process. As a result,two types of dipeptide were produced. 相似文献
10.
Jeong Hyun Kim Seung-Hyun Kang Il Nam Jung Kwan Mook Kim Bok Ryul Yoo Myong Euy Lee 《Journal of Sol-Gel Science and Technology》2004,32(1-3):31-35
Reaction of (triphenylmethyl)silanetriol (1) with cyclopentadienyltitanium trichloride (CpTiCl3) in the presence of triethylamine as a HCl scavenger gave both compounds of a partial open-cage type {[Ph3CSiO(OH)]3(Ph3CSiO3/2)(CpTiO3/2)4} (2) and cube type (Ph3CSiO3/2CpTiO3/2)4 (3). The 1:1 reaction of 1 and CpTiCl3 in toluene solvent at reflux temperature for 3 d afforded compounds 2 (22%) and 3 (36%). When 1 is reacted with a 1.5 fold excess of CpTiCl3 under the same conditions, compound 3 was obtained in high yield (81%) along with 2 in trace quantities. Compounds 2 and 3 were fully characterized by the analyses of 1H, 13C, 29Si NMR, IR, and FAB MS data. The solid-state structure of 3 was determined by a single crystal X-ray diffraction study. Compound 3 had shown to have catalytic activity for the oxidation of alkenes such as 1-octene, cyclooctene, and norbornene with t-butyl hydrogen peroxide. The effect of solvent was observed in this epoxidation reaction. The order of reactivity were decreased as follows: CHCl3 > hexane THF. 相似文献